Dyes of the anthraquinone series



Patented Feb. 21, 1933 UNITED STATES PATENT OFFICE i,

ARNOLD SHEPHERDSON' AND WILLIAM WYNDI-IAM TATUM, or 'BLACKLEY, MAN cnnsrnn, ENGLAND, Ass e ons 'ro IMPERIAL CHEMICAL INDUSTRIES LIMITED,

' or I.oN:ooN, ENGLAND DYE-S 01 THE ANrIIRAQUI oNn seams No Drawing. Application filed April 13, 1929, seriai 'No. esae'iaana'm Great Britain April 19, 192s.

This invention relates to the production of new anthraquinone dyes, and it comprises a process wherein phenylenediamine compounds are condensed with certain halogenated anthraquinones; and it further comprises the new anthraquinone" derivatives thus produced; all as more fully hereinafter set forth and as claimed. 1

"Our new anthraquinonederivatives may be represented by the probable general formula.

R i) N-RI c a e 1,.

wherein R represents hydrogen or an alkyl group, R represents. hydrogema halogen or a sulphonic group and R represents a residue having the following formula i I r x V wherein X represents hydrogen or 'a sulphonic groupand in which only one B represents said residuef We have found that such new anthraquinone derivatives may be advantageously used as dyes for various materials. The sulphonated products dye wool, silk, and cotton in valuable level and fast shades in an advantageous manner, the unsulphonated compounds especially those containing an alkyl amino group in position 1 dye cellulose esters or ethers in desirable even green shades In an advantageous manner. i in an aqueousmedium' We have I Such green shadeson cellulose esters or ethers have not hitherto been obtainable by of the anthraquinone wherein X represents hydrogen or a sulphonic group and 'Y represents hydrogen or an acyl group, with anthraquinonederiva- 'tives having the probable formula wherein R represents hydrogen or an alkyl wherein R, represents'hydrogen or an-alkyl having the following probable group, R represents hydrogen, a halogen or a sulphonic group and R represents hydrogen or a halogen and in whiohfonly 1 Rgjis a halogen. "The: said condensation may beeffound that this condensation proceeds much more 'smoothlyin an aqueous medium than Lin an organic solvent free from water. This 1s a surprising discovery as inthe usual process using simply aryl amines instead of phe nylenediamine, the condensation is effected in an organic solvent which must be free of even traces of water. The products obtained by our new method are pure and the yield is improved; an economy of materials being effected.

In carrying out our process we may use para-phenylenediamine or its mono-sulphonic acid derivative. Also the mono acylated derivative of, para-phenylenediamine, for instance the acetyl or oxyl derivatives may be used. When an acyl derivative of para-phenylenediamine is employed the acyl.

ent application-is specifically directed to the anthraquinone derivatives wherein R is a sulphonicgroup. Also in our above identified divisional application we disclose and claim the process of introducing this nuclear sulphonic group into the anthraquinone compounds.

The following typical examples illustrate our invention and serve to guide those skilled in the art in using our, broad invention to the best advantage. In the examples the parts are by weight.

Ewample 1 Preparation of l-methyl amino l-(p-amino-anilino anthraquinone.

O B T-43H:

ti EONH? A mixture of 10 parts of l-bromo-l-methyl amino anthraquinone, 6 parts of p-phenylenediamine and part of copper acetate are introduced into 90 parts of hot saturated potassium .carbonate solution (about 63 per cent). The whole is heated at 130 C. for 3 hours and is then diluted with water. The new dyestuff formed is insoluble and is filtered off and washed with dilute hydrochloric acid. When crystallized from aniline it forms green crystals insoluble in water or 1 Ewample 2 Preparation of Q-brOm -I-aminO- I-(pamino-anilino) anthraquinone.

Q V O' p O IE-O-NH:

1 0 parts of 2: 4-dibromo-Laminoanthraquinone together; with 5' parts of p-phenylenediamine and half a part of copper acetate are fed into. 90 parts of 15 per cent caustic soda solution and boiled (at about 106 C.) for 2 hours. The precipitated base after filtering and washing with dilute acid may be purified by extraction with sulphuric acid of suit able strength such as 65 per cent. It is thereby obtained in the form of a blue powder insoluble in water or alkalies but giving a re solution with hydrochloric acid. The solution in methylated spirits is blue and in sulphuric acid violet changing to bluish-green on addition of formaldehyde.

The remaining bromineatom may be readily replaced by the sulphonic acid group, for example, by heating with sodium sulphite at 165 C. in aqueous phenol solution. The resultant sulphonic acid dissolves with a blue colour in water or alkalies, the solution becoming red when strongly acidified. A solution of the sulphonated dye in methylated spirits is blue, and in sulphuric acid it'is' blue which on addition of formaldehyde changes to green. From an acidulated bath, the new sulphonic acid dyes wool in level blue to green shades ofexcellent fastness. It has the probable formula r Ewample This example gives an alternative method in Example 2 and which most probably has in the form of the sodium salt the constitution represented by the formula soma 10 parts of l-amino--bromo'anthraquinone- 2-sulphonic acid, 5 parts of p-phenylenediamine, 5 parts of soda ash and 0.2 parts of copper bronze are-boiled for a few minutes with 60 parts of water and then treated with 0.2 parts of copper acetate. vAfter boiling for 2 hours longer, the charge is acidified with acetic acid, and the crude colour filtered off and purified, for example, by extraction with dilute acid. The new dyestufi is identical in reactions with the sulphonic acid described in Example 2. I 7

Example 20 parts of 1: 5-aminochloroanthraquinone and 12 parts of p-phenylenediamine and 1 part of copper acetate are fed into a hot solution of 120 parts potassium carbonate ;in about parts water. The charge is'stirred at l25-130 C. for 3 hours then diluted with hot water and the l-amino-5-aminoanilinoanthraquinone filtered off. It may be purified by extraction with dilute hydrochloric acid and crystallized from aniline. It forms bluish red crystals which dissolve in sulphuric acid giving a green coloured solution addition of formaldehyde changes this green colour to a bright blue. A solution of this dye in methylated spirit is bluish red. It has the probable formula What we claim and desire to secure by Letters Patent is:

1. In the manufacture ofnew anthraquinone dyestuffs, the process which comprises condensing a phenylenediamine compound having the probable formula IlC H wherein X represents hydrogen or a sulphonic group and Y represents hydrogen or an acyl group, wlth a halogenated anthraquinone compound having the probableformula .whereinR representsihydrogen onan alkyl group, R represents hydrogen, a halogen or a sulphonic group, andR represents hydro gen or a halogen, and in which only one R is a halogen, said condensation being effected in an alkalinaqueous medium. 2. In the manufacture of new anthraquinone dyestuffs, the process which comprises condensing paraphenylenediamine with a halogenated anthraquinonecompound having the probable formula wherein R represents hydrogen or an alkyl group, R represents hydrogen, a halogen or a sulphonic group, and R represents hydrogen or a halogen, and in which only one It,-

is a halogen, said" condensation being effected in an alkalin aqueous medium.

' 3. In the manufacture of new anthraquinone dyestuffs, theprocess whichv comprises mixing together, in an aqueous medium, paraphenylenediamine and a halogenated anthraquinone compound having the probable formula V I pounds suitable as dyestuffs and having the probable formula o/ R t wherein R represents hydrogen or an alkyl group and R and R represent hydrogen or a residue having the probable formula NO-NH2 V and which contains only one such residue and in which R represents an alkyl group when R represents said residue, the said anthraquinone compounds dyeing acetate silk in even blue to green shades.

6. As new products, anthraquinone compounds suitable as dyestuffs and having the probable formula wherein R represents hydrogen or an alkyl group, R represents hydrogen, a halogen or a sulphonic group and in which R represents an alkyl group when R represents hydrogen, the said anthraquinone compounds being'soluble in concentrated sulphuric acid, giving solutions varying from purple through blue to green in color, and being soluble in methylated spirit, giving blue to reddish blue solutions, the said anthraquinone compounds dyeing acetate silk and wool in bluish green to green shades.

7 As new products, anthraquinone compounds suitable as dyestuffs and having the probable formula t ,I M.

wherein R represents hydrogen or an alkyl group, R represents hydrogen or a halogen and in which R represents an alkyl group when R represents a hydrogen, the said anthraquinone compounds being soluble in concentrated sulphuric acid and in methylates spirit, the said anthraquinone compounds dyeing acetate silk in bluish green to green shades.

8. As a new product an anthraquinone compound suitable as a dyestuif and as an iritermediate and havingthe probable formu a o N-OHI.

/g\ I w O i p o EONHQ said anthraquinone compound occurring-as green crystals insoluble in water or alkalies, dissolving in concentrated hydrochloric acid to give a red solution and in acetic acid or lution, and dissolving in sulphuric acid to give a purple solution which on the addition of formaldehyde changes to'bluish-green, the said dyestuif dyeing acetate silk in bluishgreen shades.

9. In the manufacture of new anthraquinone dyestuffs, the process which comprises condensing paraphenylenediamine with an anthraquinone compound having the probable formula V E r rrn' -SOaH 0 B: said condensation beingeffected in an alkalin aqueous solution, and recovering the condensation product thus produced, sa1d condensation product being suitable as a dyestuff. 11. In the manufacture of new anthraquinone dyestuffs, the process which commethylated spirit to give a greenish-blue soteams prises p condensing. paraphenylenediamine with an anthraquinone compound having the probable formula 1 and recovering the condensationproduct thus 7 produced, said condensation product being suitable as a dyestuif and as anintermediate.

12. In-the manufacture of new anthraquinone dyestuffs, the process which comprises with an anthraquinone compound having the probable formula and recovering the condensation product thus produced, said condensation product being suitable as a dyestufi'.

13. As new products, anthraquinone com pounds suitable as dyestuffs and as intermediates and having the probable formula wherein R represents hydrogen or a methyl group, R represents hydrogen, bromine or a sulphonic group and R and R" represent hydrogen or the residue and in which R represents a methyl group when R and R represent hydrogen and said residue, respectively, the said compound hav ing one and only one such residue.

14. As a new product an anthraquinone compound suitable as a dyestufl and as an intermediate and having the probable formula NHQ

said anthraquinone compound occurring as bluish red crystals dissolving in sulphuric condensing paraphenylenediamine i acid to give a green colored solution which on the addition of'formaldehyde changes to a bright blue and dissolving in methylated spirit giving a bluish red solution.

15. As a new product, an anthraquinone compound suitable as a dyestuif and as an intermediate and having the probable formula V I o NH: 1

Br L said'anthraquinone compound being a blue powder insoluble in water or alka1ies,"*dissolving infhydrochloric acid to give 'a'red solution and in methylated spirit to give a blue solution, and dissolving in sulphuric acid 'togive a violet solution which on the addition of formaldehyde changes'to bluish green.

16. In the manufacture of new anthraquinone. dyestuffs, the process which'comprises condensing, paraphenylenediamine w th a halogenated anthraqulnone compound having the probable formula wherein R represents hydrogen or a methyl group, R represents hydrogen, bromine or asulphonic group and R represents hydrogen or a halogen, one R being hydrogen, and

the other being a halogen said condensation being effected in an alkalin aqueous solution, and recovering the condensation product thus produced, said condensation product being suitable as a'dyestufl'. Y A e j v 17 As new products, suitable as dyestuffs and as intermediates, the anthraquinone comas intermediates by processes involving con densing paraphenylenediamine compounds with halogenated anthraquinone compounds, the steps which comprise mixing together about 10 parts of l-bromo-l-methylamino anthraquinone, about 6 parts of paraphenylenediamine 'and a small "amount'of copper.

acetate, in a hot saturated potassium carbonate .solution, heating the aqueous mixture thus obtained to about 130 C. until reaction and condensation are effected, diluting the reaction mixture with water and isolating and recovering the anthraquinone compound thus obtained, said compoundhaving a good afiinity for acetate silk which is dyed by it to bluish green shades of excellent fastness.

19. In the manufacture of new anthraquinone compounds suitable as dyestuffs and as intermediates by processes involving condensing paraphenylenediamine compounds with halogenated a-nthraquinone compounds, the steps which comprise mixing together about 10 parts of 234 dibromo-l-amino-anthraquinone, about 5 parts of paraphenylenediamine and a small amount of copper ace tate, in .a caustic soda solution, boiling the aqueous mixture thus obtained until'reaction and condensation areefli'ected, and then isolating and recoverlng .the anthraqumone compound thus obtained in the form of a blue powder insoluble in water.

20. In the manufacture of new anthraquinone compounds suitable as dyestufi's and as intermediates by processes involving condensing paraphenylenediamine. compounds 7 with halogenated anthraquinone compounds, 1 the steps which comprise mixing together about 10 parts of 1-aminoi-bromo-anthraquinone-Q-sulphonic acid, about 5 parts of paraphenylenediamine and-a small amount of copper bronze and copper acetate, in an aqueous solution of soda ash, boiling the ing theaqueous mixture thus obtained at be. '50

aqueous mixture thus obtained until reaction and condensation are effected, and then isolating and recovering the anthraquinone, compound thus obtained.

21. In the manufacture of new anthraquinone compounds suitable as dyestufi's and as intermediates by processes involving condensing paraphenylenediamine compounds with halogenated anthraquinone compounds, the

steps which comprise mixing together about 20 parts of 1:5 aminochloro-anthraquinone, about 12 parts of paraphenylenediamine and a small amount of copper acetate in'a hot aqueous solution of potassium carbonate,heat

tween 125 and 130 C. until reaction and condensation are efi'ected, diluting the aqueous :reaction mixture thus obtained with hot water and then isolating and recovering the anthraquinone compound thus produced.

22. In the manufacture of new anthraquinone compounds suitable as dyestufl's and i as intermediates by processes involving condenslng paraphenylenediamine compounds with halogenated anthraquinone compounds,

product thus obtained from the aqueous re- 1 action mixture.

In testimony whereof we aflix our signatures.

ARNOLD SHEPHERDSON. WILLIAM WYNDHAM TATUM. 

